Porous amorphous silicon-carbon nanotube composite based electrodes for battery applications

ABSTRACT

Embodiments of the present invention generally relate to methods and apparatus for forming an energy storage device. More particularly, embodiments described herein relate to methods of forming electric batteries and electrochemical capacitors. In one embodiment a method of forming a high surface area electrode for use in an energy storage device is provided. The method comprises forming an amorphous silicon layer on a current collector having a conductive surface, immersing the amorphous silicon layer in an electrolytic solution to form a series of interconnected pores in the amorphous silicon layer, and forming carbon nanotubes within the series of interconnected pores of the amorphous silicon layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. provisional patent applicationSer. No. 61/239,515 (Attorney Docket No. 14153L), filed Sep. 3, 2009,which is herein incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the present invention generally relate to methods offorming an energy storage device. More particularly, embodimentsdescribed herein relate to methods of forming electric batteries andelectrochemical capacitors.

2. Description of the Related Art

Fast-charging, high-capacity energy storage devices, such assupercapacitors and lithium (Li+) ion batteries, are used in a growingnumber of applications, including portable electronics, medical,transportation, grid-connected large energy storage, renewable energystorage, and uninterruptible power supply (UPS) applications. In each ofthese applications, the charge time and capacity of energy storagedevices are important parameters. In addition, the size, weight, and/orexpense of such energy storage devices can be significant limitations.Further, low internal resistance is necessary for high performance. Thelower the resistance, the less restriction the energy storage deviceencounters in delivering electrical energy. For example, in the case ofsuper capacitors, lower internal resistance allows faster and moreefficient charging and discharging thereof. In the case of a battery,internal resistance in a battery impacts performance by reducing thetotal amount of useful energy stored by the battery as well as theability of the battery to deliver the high current pulses demanded bydigital devices.

Accordingly, there is a need in the art for faster charging, highercapacity energy storage devices that are smaller, lighter, have a longercycle life, and can be more cost effectively manufactured. There is alsoa need in the art for components for an electrical storage device thatreduce the internal resistance of the storage device.

SUMMARY OF THE INVENTION

Embodiments of the present invention generally relate to methods offorming an energy storage device. More particularly, embodimentsdescribed herein relate to methods of forming electric batteries andelectrochemical capacitors. In one embodiment a high surface areaelectrode for use in an electrochemical device is provided. The highsurface area electrode comprises a substrate having a conductivesurface, a porous amorphous silicon layer on the conductive surface ofthe substrate, wherein the porous amorphous silicon layer has a seriesof interconnected pores, and carbon nanotubes embedded within the seriesof interconnected pores of the amorphous silicon layer.

In another embodiment, a high surface area electrode for use in anenergy storage device is provided. The high surface area electrodecomprises a substrate having a conductive surface and a porous amorphoussilicon carbon nanotube composite based material deposited on theconductive surface. The porous amorphous silicon carbon nanotubecomposite based material deposited on the conductive surface comprises aporous amorphous silicon layer formed on the conductive surface of thesubstrate, wherein the porous amorphous silicon layer has a series ofinterconnected pores and carbon nanotubes embedded within the series ofinterconnected pores of the porous amorphous silicon layer.

In yet another embodiment, a method of forming a high surface areaelectrode for use in an energy storage device is provided. The methodcomprises forming an amorphous silicon layer on a current collectorhaving a conductive surface, immersing the amorphous silicon layer in anelectrolytic solution to form a series of interconnected pores in theamorphous silicon layer, and forming carbon nanotubes within the seriesof interconnected pores of the amorphous silicon layer.

In yet another embodiment a method of fabricating a high surface areaelectrode is provided. The method comprises depositing an aluminumsilicon matrix on a substrate, removing the aluminum from the siliconmatrix to form a porous silicon layer having a plurality of pores, andgrowing carbon nanotubes in the plurality of pores in the porous siliconlayer to form a silicon carbon nanotube matrix.

In yet another embodiment, an apparatus for fabricating a high surfacearea electrode, comprising a first end, a second end, at least one webof material extending from the first end to the second end, a supportsystem to support the at least one web of material from the first end tothe second end, and a plurality of chambers disposed between the firstand the second end, the plurality of chambers being adapted andconfigured to form the high surface area electrode on the at least oneweb of material, wherein the at least one web of material extendsthrough the plurality of chambers.

In yet another embodiment, an apparatus for forming an energy storagedevice on a substrate comprising at least one continuous web ofconductive material is provided. The apparatus comprises a first end, asecond end, a support system to support the at least one continuous webof conductive material extending from the first end to the second end, afirst chamber disposed between the first and the second end fordepositing an amorphous silicon layer on the at least one continuous webof conductive material, wherein the first chamber comprises, and asecond chamber disposed between the first end and the second end forexposing the amorphous silicon layer to an anodization process, whereinthe second chamber, comprises. The first chamber comprises a hotfilament adapted to be heated at a surface temperature higher than1,500° C., a showerhead that is adapted to deliver a silicon containinggas to form the amorphous silicon layer on the at least one continuousweb of conductive material using a hot wire chemical vapor deposition(HWCVD) process, and a silicon containing gas source coupled with theshowerhead for delivery of the silicon containing gas to the showerhead.The second chamber comprises a processing volume adapted to hold anelectrolytic solution, an anode assembly disposed in the electrolyticsolution, wherein the anode assembly is movable to contact the substrateand anodically bias the substrate, a cathode assembly disposed in theelectrolytic solution, one or more inlet jets configured to dispense theelectrolytic solution into the processing volume, and a power supplyadapted to deliver power to the anode assembly and the cathode assemblysuch that the amorphous silicon layer is anodized to form aninterconnected porous amorphous silicon layer.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentinvention can be understood in detail, a more particular description ofthe invention, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIG. 1 is a schematic diagram of one embodiment of a Li-ion batteryelectrically connected to a load;

FIGS. 2A-2D are schematic cross-sectional views of one embodiment of ahigh surface area electrode formed in accordance with embodimentsdescribed herein;

FIG. 3 is a schematic cross sectional view of one embodiment of anamorphous silicon layer having interconnected pores formed according toembodiments described herein;

FIG. 4 is a schematic cross sectional view of one embodiment of a porousamorphous silicon carbon nanotube composite based material formedaccording to embodiments described herein;

FIG. 5A is a schematic view of one embodiment of a single-walled carbonnanotube;

FIG. 5B is a schematic view of one embodiment of a multi-walled carbonnanotube;

FIG. 6 is a process flow chart summarizing one embodiment of a methodfor forming a high surface area electrode according to embodimentsdescribed herein;

FIGS. 7A-7G are schematic cross-sectional views of one embodiment of ahigh surface area electrode formed in accordance with embodimentsdescribed herein;

FIG. 8 is a process flow chart summarizing one embodiment of a methodfor forming a high surface area electrode according to embodimentsdescribed herein;

FIGS. 9A-9D are schematic isometric views of one embodiment of a highsurface area electrode formed in accordance with embodiments describedherein;

FIG. 10 is a process flow chart summarizing one embodiment of a methodfor forming a high surface area electrode according to embodimentsdescribed herein;

FIG. 11 is a schematic plan view of one embodiment of a processingsystem that may be used to form the high surface area electrodesdiscussed herein;

FIG. 12 is a schematic side view of one embodiment of an apparatus forforming a high surface area electrode on substrates in the form of aweb, showing the various chambers for forming the high surface areaelectrode;

FIG. 13 is a schematic side view of one embodiment of a chamber fordepositing amorphous silicon on a substrate;

FIG. 14 is a schematic side view of one embodiment of a chamber forperforming an anodization process on a substrate;

FIG. 15A is a schematic side view of one embodiment of a chamber fordepositing catalyst material on a substrate;

FIG. 15B is a schematic side view of another embodiment of a chamber fordepositing catalyst material on a substrate; and

FIG. 16 is a schematic side view of one embodiment of a chamber fordepositing carbon nanotubes on a substrate.

DETAILED DESCRIPTION

Embodiments of the present invention generally relate to methods offorming an energy storage device. More particularly, embodimentsdescribed herein relate to methods of forming electric batteries andelectrochemical capacitors. In one embodiment, a composite electrodecomprising carbon or carbon nanotubes deposited in the pores of anamorphous silicon thin film is provided for use in Li-ion batterysystems. In one embodiment, amorphous silicon is deposited on asubstrate of interest (e.g., silicon, semiconductor wafer, stainlesssteel, or oxides) using chemical vapor deposition (CVD) techniques, suchas plasma enhanced chemical vapor deposition (PECVD), or hot-wirechemical vapor deposition (HWCVD) technique at low temperatures. Inanother embodiment, instead of depositing amorphous silicon, ananocrystalline/polycrystalline silicon wafer may be bombarded with ionsto from amorphous silicon. In one embodiment, the amorphous silicon thinfilm is anodized to form pores in the amorphous silicon thin film. Inone embodiment, the anodization is carried out in an electrochemicalbath. In one embodiment, the electrochemical bath comprises hydrofluoricacid (HF) and acetic acid. In one embodiment, the electrochemical bathcomprises 50% HF(49%)/50% acetic acid (glacial). In one embodiment, theanodization process if performed at room temperature at currentdensities between 20 mA/cm² and 100 mA/cm².

In one embodiment, the pore size is uniform. In another embodiment, thesize of the pores is varied by varying the voltage applied during theanodization process. In one embodiment, the size of the pores formed inthe anodization process is varied from 20 nm to 1,000 nm by changing thecurrent density resulting in either through pores or inter-networkedpores in the amorphous silicon structure.

In one embodiment, carbon nanotubes (CNTs) are formed in the pores usingCVD processes. In one embodiment, the temperature during the CVDdeposition of the CNTs is varied between about 500° C. and about 800° C.using different carbon source precursors such as methane, acetylene,xylene, and octane. In one embodiment, the final electrode structure hasa current collector with the porous amorphous silicon and CNTs embeddedor grown in the pores of the amorphous silicon. The amorphous siliconhelps in the higher energy density when it interacts with Li ions whilethe intercalation of Li ion will help in increasing the cyclability andpower density.

While the particular apparatus in which the embodiments described hereincan be practiced is not limited, it is particularly beneficial topractice the embodiments in a cluster tool system or a web-basedroll-to-roll system sold by Applied Materials, Inc., Santa Clara, Calif.Exemplary roll-to-roll and discrete substrate systems on which theembodiments described herein may be practiced are described in furtherdetail in commonly assigned U.S. Provisional Patent Application Ser. No.61/243,813, (Attorney Docket No. APPM/014044/ATG/ATG/ESONG), filed Sep.18, 2009, titled APPARATUS AND METHODS FOR FORMING ENERGY STORAGE OR PVDEVICES IN A LINEAR SYSTEM, which is herein incorporated by reference inits entirety.

FIG. 1 is a schematic diagram of one embodiment of a Li-ion battery 100electrically connected to a load 101, according to embodiments describedherein. The primary functional components of Li-ion battery 100 includean anode structure 102, a cathode structure 103, a separator layer 104,and an electrolyte (not shown) disposed within the region between theopposing current collectors 111 and 113. A variety of materials may beused as the electrolyte, such as lithium salts in an organic solvent.The electrolyte is contained in anode structure 102, cathode structure103, and a fluid-permeable separator layer 104 in the region formedbetween the current collectors 111 and 113.

The anode structure 102 and the cathode structure 103 each serve as ahalf-cell of the Li-ion battery 100 and together form a complete workingcell of the Li-ion battery 100. The anode structure 102 includes acurrent collector 111 and a porous amorphous silicon carbon nanotubecomposite based material 110 that acts as a carbon-based intercalationhost material for retaining lithium ions. Similarly, cathode structure103 includes a current collector 113 and an intercalation host material112 for retaining lithium ions, such as a metal oxide. Separator layer104 is a dielectric, porous, fluid-permeable layer that prevents directelectrical contact between the components in the anode structure 102 andthe cathode structure 103. Methods of forming Li-ion battery 100, aswell as the materials that make up the constituent parts of Li-ionbattery 100, i.e., anode structure 102, cathode structure 103, andseparator layer 104, are described below.

Rather than the traditional redox galvanic action of a conventionalsecondary cell, Li-ion secondary cell chemistry depends on a fullyreversible intercalation mechanism, in which lithium ions are insertedinto the crystalline lattice of an intercalation host material in eachelectrode without changing the crystal structure of the intercalationhost material. Thus, it is necessary for such intercalation hostmaterials in the electrodes of a Li-ion battery to have open crystalstructures that allow the insertion or extraction of lithium ions andhave the ability to accept compensating electrons at the same time. InLi-ion battery 100, the anode, or negative electrode, is based oncarbon, i.e., the porous amorphous silicon carbon nanotube compositebased material 110. The cathode, or positive electrode, is made from ametal oxide, such as lithium cobalt dioxide (LiCoO₂) or lithiummanganese dioxide (LiMnO₂). The cathode may be made from a layeredoxide, such as lithium cobalt oxide, a polyanion, such as lithium ironphosphate, a spinel, such as lithium manganese oxide, or TiS₂ (titaniumdisulfide). Exemplary oxides may be layered lithium cobalt oxide, ormixed metal oxide, such as LiNi_(x)Co_(1-2x)MnO₂, LiMn₂O₄. Exemplaryphosphates may be iron olivine (LiFePO₄) and it is variants (such asLiFe_(1-x)MgPO₄), LiMoPO₄, LiCoPO₄, Li₃V₂(PO₄)₃, LiVOPO₄, LiMP₂O₇, orLiFe_(1.5)P₂O₇. Exemplary fluorophosphates may be LiVPO₄F, LiAlPO₄F,Li₅V(PO₄)₂F₂, Li₅Cr(PO₄)₂F₂, Li₂CoPO₄F, Li₂NiPO₄F, or Na₅V₂(PO₄)₂F₃.Exemplary silicates may be Li₂FeSiO₄, Li₂MnSiO₄, or Li₂VOSiO₄.

The separator layer 104 is configured to supply ion channels formovement between the anode structure 102 from the cathode structure 103while keeping the anode structure 102 and the cathode structure 103physically separated to avoid a short. In one embodiment, the separatorlayer 104 may be deposited onto the surface of the porous amorphoussilicon carbon nanotube composite based material 110 and may be a solidpolymer, such as polyolefin, polypropylene, polyethylene, andcombinations thereof.

In operation, Li-ion battery 100 provides electrical energy, i.e.,energy is discharged, when the anode structure 102 and the cathodestructure 103 are electrically coupled to load 101, as shown in FIG. 1.Electrons originating from the porous amorphous silicon carbon nanotubecomposite based material 110 flow from the current collector 111 of theanode structure 102 through the load 101 and the current collector 113to the intercalation host material 112 of the cathode structure 103.Concurrently, lithium ions are dissociated, or extracted, from theporous amorphous silicon carbon nanotube composite based material 110 ofthe anode structure 102, and move through the separator layer 104 intothe intercalation host material 112 of the cathode structure 103 and areinserted into the crystal structure of the intercalation host material112. The electrolyte, which resides in the porous amorphous siliconcarbon nanotube composite based material 110, intercalation hostmaterial 112, and the separator layer 104, allows the movement oflithium ions from the porous amorphous silicon carbon nanotube compositebased material 110 to the intercalation host material 112 via ionicconduction. The Li-ion battery 100 is charged by electrically couplingan electromotive force of an appropriate polarity to the anode structure102 and the cathode structure 103 in lieu of the load 101. Electronsthen flow from the current collector 113 of the cathode structure 103 tothe current collector 111 of the anode structure 102, and lithium ionsmove from the intercalation host material 112 in the cathode structure103, through the separator layer 104, and into the mesoporous carbonmaterial 110 of the anode structure 102. Thus, lithium ions areintercalated into the cathode structure 103 when Li-ion battery 100 isdischarged and into the anode structure 102 when the Li-ion battery 100is in the charged state.

FIGS. 2A-2D are schematic cross-sectional views of a high surface areaelectrode 200 formed in accordance with embodiments described herein. InFIG. 2A, the current collector 111 is schematically illustrated prior tothe formation of the porous amorphous silicon carbon nanotube compositebased material 110. The current collector 111 may include a relativelythin conductive layer disposed on a host substrate, or simply aconductive substrate (e.g., foil, sheet, plate), comprising one or moreconductive materials, such as a metal, plastic, graphite, polymers,carbon-containing polymer, composites, or other suitable materials.Examples of metals that the current collector 111 may be comprised ofinclude copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), palladium(Pd), platinum (Pt), tin (Sn), ruthenium (Ru), stainless steel, alloysthereof, and combinations thereof. In one embodiment, the currentcollector 111 is a metallic foil and may have an insulating coatingdisposed thereon. Alternatively, the current collector 111 may comprisea host substrate that is non-conductive, such as a glass, silicon,plastic, or polymeric substrate that has an electrically conductivelayer formed thereon by means known in the art, including physical vapordeposition (PVD), electrochemical plating (ECP), electroless plating,and the like. In one embodiment, the current collector 111 is formed outof a flexible host substrate. The flexible host substrate may be alightweight and inexpensive plastic material, such as polyethylene,polypropylene or other suitable plastic or polymeric material, with aconductive layer formed thereon. Materials suitable for use as such aflexible substrate include a polyimide (e.g., KAPTON™ by DuPontCorporation), polyethyleneterephthalate (PET), polyacrylates,polycarbonate, silicone, epoxy resins, silicone-functionalized epoxyresins, polyester (e.g., MYLAR™ by E.I. du Pont de Nemours & Co.),APICAL AV manufactured by Kanegaftigi Chemical Industry Company, UPILEXmanufactured by UBE Industries, Ltd.; polyethersulfones (PES)manufactured by Sumitomo, a polyetherimide (e.g., ULTEM by GeneralElectric Company), and polyethylenenaphthalene (PEN). Alternately, theflexible substrate may be constructed from a relatively thin glass thatis reinforced with a polymeric coating.

In FIG. 2B, an amorphous silicon layer 204 is formed over the currentcollector 111. In one embodiment, the amorphous silicon layer 204 has athickness from about 100 nm to about 3 μm. In one embodiment, theamorphous silicon layer 204 has a thickness from about 500 nm to about 2μm. In one embodiment, the amorphous silicon layer has a thickness fromabout 700 nm to about 1000 nm. In one embodiment, the amorphous siliconlayer 204 is deposited using a chemical vapor deposition process such asplasma enhanced chemical vapor deposition (PECVD) or hot-wire chemicalvapor deposition (HWCVD). In one embodiment ananocrystalline/polycrystalline layer is formed over the currentcollector 111 and subsequently bombarded with ions to form the amorphoussilicon layer 204.

In FIG. 2C, a porous amorphous silicon layer 206 is formed over thecurrent collector 111. In one embodiment, the porous amorphous siliconlayer 206 is formed by exposing the amorphous silicon layer 204 to ananodization process to form interconnected pores 208. In one embodiment,each of the interconnected pores 208 has a diameter from about 20 nm toabout 1,000 nm. In one embodiment, each of the interconnected pores hasa diameter from about 100 nm to about 500 nm. In one embodiment, each ofthe interconnected pores has a diameter from about 100 nm to about 200nm. In one embodiment, each of the interconnected pores has a diameterfrom about 30 nm to about 50 nm. In one embodiment, the interconnectedpores 208 are through pores extending from a top surface 210 of theporous amorphous silicon layer 206 to a bottom surface 211 of the porousamorphous silicon layer 206 exposing a top surface 214 of the currentcollector 111. In one embodiment, the interconnected pores 208 extendfrom the top surface 210 of the porous amorphous silicon layer 206stopping at a distance from the bottom surface 211 of the porousamorphous silicon layer 206. In one embodiment, the interconnected pores208 extend from the top surface 210 of the porous amorphous siliconlayer 206 to from about 10 nm to about 200 nm from the bottom surface211 of the porous amorphous silicon layer 206. In one embodiment thediameter of the pore 208 may vary along the length of the pore 208. Inone embodiment, the diameter of the pore decreases along the length ofthe pore 208 from the top surface 210 of the porous amorphous siliconlayer 206 to the bottom surface 211 of the porous amorphous siliconlayer 206. In one embodiment, the diameter of the pore increases alongthe length of the pore 208. In one embodiment, the interconnected pores208 comprise a series of interconnected branch structures havingbranches of varying lengths and diameters. In one embodiment, thediameter of the interconnected pores 208 decreases as the interconnectedpores 208 extend downward from the top surface 210 of the porousamorphous silicon layer 206 toward the bottom surface 211 of the porousamorphous silicon layer 206. In one embodiment the length of each pore208 is equivalent to the thickness of the film. In one embodiment, thelength of each pore 208 is between about 0.5 microns and about 5millimeters. In another embodiment, the length of each pore 208 isbetween about 100 microns and about 500 microns. In another embodiment,the length of each pore 208 is about 200 microns. In one embodiment, theporous amorphous silicon layer 206 may have a porosity that is between50%-90% as compared to a solid film formed from the same material.

In FIG. 2D, a carbon structure such as carbon nanotubes are formedwithin the interconnected pores 208 to form the porous amorphous siliconcarbon nanotube composite based material 110. In one embodiment, thecarbon nanotubes are formed along the walls 216 of the interconnectedpores 208. In one embodiment, the carbon nanotubes extend above the topsurface 210 of the porous amorphous silicon carbon nanotube compositebased material 110.

FIG. 3 is a schematic cross sectional view of one embodiment of anamorphous silicon layer 302 having interconnected pores 306 formedaccording to embodiments described herein that may make up the porousamorphous silicon carbon nanotube composite based material 110. Theamorphous silicon layer 302 has a top surface 308 and a bottom surface310. The interconnected pores may comprise cylindrical holes, each holehaving a diameter “d_(h)” which ranges from a few nanometers to hundredsof nanometers and a depth “D” which may range from a few micrometers tohundreds of micrometers. The series of interconnected pores 306comprises a plurality of individual pores of varying lengths anddiameters. In one embodiment, a first pore 312 extends from the topsurface 308 and has a first diameter 314. In one embodiment, the firstdiameter is from about 500 nm to about 1000 nm. In one embodiment, thefirst diameter is from about 700 nm to about 900 nm.

The first pore 312 extends downward toward the bottom surface 310forming first branch structures 316 a, 316 b. At the first branchstructures 316 a, 316 b the first pore 312 splits into multiple pores318 a, 318 b, 318 c having a second diameter 320. In one embodiment, thesecond diameter is less than the first diameter 314. In one embodiment,the second diameter 320 is from about 200 nm to about 500 nm. In oneembodiment, the second diameter 320 is from about 300 nm to about 400nm. Although the first pore 312 is depicted as splitting into threepores 318 a, 318 b, 318 c, it should be understood that the first pore312 may split into any number of pores and each pore may having similaror different diameters.

Each of the multiple pores 318 a, 318 b, 318 c, extends downward towardthe bottom surface 310 forming a second branch structure 324 a, 324 b.At the second branch structure 324 a, 324 b each of the multiple pores318 a, 318 b, 318 c splits into multiple pores 326 a, 326 b, 326 chaving a third diameter 328. In one embodiment, the third diameter isless than the second diameter 320. In one embodiment, the third diameteris from about 20 nm to about 200 nm. In one embodiment, the thirddiameter is from about 50 nm to about 100 nm.

In one embodiment, the interconnected pores 306 are through poresextending from the top surface 308 of the amorphous silicon layer 302 tothe bottom surface 310 of the amorphous silicon layer 302. In oneembodiment, the interconnected pores 306 extend from the top surface 308of the porous amorphous silicon layer 302 to an average distance 330from the bottom surface 310 of the porous amorphous silicon layer 302.In one embodiment the average distance 330 is from about 10 nm to about200 nm. In one embodiment, the average distance 330 is from about 50 nmto about 100 nm.

FIG. 4 is a schematic cross sectional view of one embodiment of a porousamorphous silicon carbon nanotube composite based material 110 formedaccording to embodiments described herein. In one embodiment, carbonnanotubes 410 are formed within the interconnected pores 306 to form theporous amorphous silicon carbon nanotube composite based material 110.In one embodiment, the carbon nanotubes are formed along the walls 412of the interconnected pores 306. In one embodiment, the carbon nanotubesextend above the top surface 308 of the porous amorphous silicon carbonnanotube composite based material 110. The carbon nanotubes 410 may haveany orientation relative to each other. In one embodiment, the carbonnanotubes 410 may be perpendicular relative to each other. In anotherembodiment, the carbon nanotubes 410 may be parallel to each other. Inone embodiment, there is one carbon nanotube per pore since the carbondeposits along the walls 412 of the pores 306.

The carbon nanotubes and/or carbon nanofibers are graphiticnanofilaments having diameters similar to that of the pore in which thenanotube is grown. For example, in embodiments where the interconnectedpores 208 have a diameter from about 20 nm to about 1,000 nm, the carbonnanotube grown within the pore 208 would also have a diameter betweenabout 20 nm to about 1,000 nm. In one embodiment, each of the carbonnanotubes has a diameter from about 100 nm to about 500 nm. In oneembodiment, each of the carbon nanotubes has a diameter from about 100nm to about 200 nm. In one embodiment, each of the carbon nanotubes hasa diameter from about 30 nm to about 50 nm. In one embodiment, thecarbon nanotubes and/or carbon nanofibers have a diameter between about0.4 nanometers to about 100 nanometers and lengths which typically rangefrom a few micrometers to a few millimeters. Graphitic nanofilaments maybe categorized according to at least four distinct structural types,namely, tubular, herringbone, platelet, and ribbon. The term “nanotube”may be used to describe the tubular structure whereas “nanofiber” maydescribe the non-tubular forms.

Carbon nanotubes are generally classified as single-walled carbonnanotubes and multi-walled carbon nanotubes. FIG. 5A is a schematic viewof a single-walled carbon nanotube (SWCNT). The SWCNT 500 is a graphiticnanofilament which comprises a cylindrical carbon molecule that may beconceptualized as a one-atom thick sheet of graphite called graphenerolled into a seamless graphene tube 504 of diameter “d” and filamentlength “L.” The graphene tube 504 forms a cylindrical wall which isparallel to the filament axis direction. One or more of the nanotubeends 502 may be capped by additional carbon atoms. The diameter “d” mayrange from about 0.4 nanometers to a few nanometers and the filamentlength “L” may range from a few micrometers to a few millimeters, andthe large length-to-diameter aspect ratio of the SWCNT 500 gives thenanotube a large surface area-to-volume ratio.

The rolled graphene layer or sheet of the SWCNT 500 comprises six-memberhexagonal rings of carbon atoms held together by covalent sp² bonds andthese bonds combined with the tubular graphene structure impartextraordinary strength (tensile strength) and stiffness (elasticmodulus) to carbon nanotubes. The SWCNT 500, for example, may have anaverage tensile strength of about 30 GPa and an elastic modulus of about1 TPa compared to stainless steel which may have a tensile strength ofabout 1 GPa and an elastic modulus of about 0.2 TPa. Carbon nanotubesalso have a fairly low density for a solid (about 1.3 g/cm³ for SWCNTs500) and their strength-to-weight ratio is the highest of knownmaterials. The electrical conductivity of the SWCNT 500 may besemiconducting or metallic depending upon how the graphene sheet isrolled to form the graphene tube 504, and metallic-type carbon nanotubescan carry electrical current densities orders of magnitude larger thanthose carried by the best conducting metals.

FIG. 5B is a schematic view of a multi-walled carbon nanotube (MWCNT).The MWCNT 510 may be conceptualized as one or more graphene tubes 504 offilament length “L” coaxially arranged about the SWCNT 500 of diameter“d.” The graphene tubes 504 form cylindrical walls which are parallel tothe filament axis direction “A” and the walls are separated from eachother by an interlayer spacing 515 of about 0.34 nanometers whichapproximates the distance between graphene layers in graphite. Thenumber of tubes (three are shown) or cylindrical walls within the MWCNT510 may range from two to fifty, or more. An outer nanotube 512 has afilament diameter “d_(o)” which may range from a few nanometers toseveral hundred nanometers or more depending upon the number of wallswithin the MWCNT 510.

The term “carbon nanotube” is typically used to describe a nanofilamentwhich comprises one or more graphene layers or sheets which are parallelto the filament axis and which form tubular structures. The term “carbonnanofiber,” on the other hand, typically describes a nanofilament whichcomprises graphene layers which may or may not be parallel to thefilament axis and which do not form tubular structures, although thestructures may be formed so that the nanofibers are substantially roundor polygonal in cross-section. Examples of nanofiber structures includeherringbone, platelet, ribbon, stacked-cone, and other carbon nanofiberstructures known in the art. Some nanofibers may have a hollow core orcentral hole along the filament axis of each nanofiber, while othernanofibers may have solid cores. The term “graphitic nanofilament” isused herein to refer to a carbon nanotube and/or carbon nanofiber. Thegraphitic nanofilaments may have overall shapes which include but arenot limited to straight, branched, twisted, spiral, and helical.Exemplary carbon nanotube and nanofiber structures are described incommonly assigned U.S. patent application Ser. No. 12/634,095, filedDec. 9, 2009, titled THREE DIMENSIONAL BATTERY WITH HYBRID NANO-CARBONLAYER, which is incorporated by reference herein.

FIG. 6 is a process flow chart summarizing one embodiment of a method600 for forming a high surface area electrode 200 according to oneembodiment described herein. In block 602, a current collector similarto current collector 111 is provided. In one embodiment, the currentcollector may include a relatively thin conductive layer disposed on ahost substrate, or simply a conductive substrate (e.g., foil, sheet,plate), comprising one or more conductive materials, such as a metal,plastic, graphite, polymers, carbon-containing polymer, composites, orother suitable materials. In one embodiment, the current collector is ametallic foil and may have an insulating coating disposed thereon. Inone embodiment, the insulating coating may comprise an oxide containinglayer such as a silicon oxide containing layer. Alternatively, thecurrent collector may comprise a host substrate that is non-conductive,such as a glass, silicon, plastic, or polymeric substrate that has anelectrically conductive layer formed thereon by means known in the art,including physical vapor deposition (PVD), electrochemical plating(ECP), electroless plating, and the like. In one embodiment, the currentcollector is formed out of a flexible host substrate.

In block 604, an amorphous silicon layer similar to amorphous siliconlayer 204 is formed on the current collector. In one embodiment, theamorphous silicon layer is deposited using a chemical vapor depositionprocess known in the art such as plasma enhanced chemical vapordeposition (PECVD) or hot-wire chemical vapor deposition (HWCVD). In oneembodiment the amorphous silicon layer is formed by depositing ananocrystalline/polycrystalline layer over the current collector 111 andsubsequently bombarding the nanocrystalline/polycrystalline layer tomodify the ordered crystal structure forming an amorphous siliconstructure.

In block 606, a porous amorphous silicon layer similar to the porousamorphous silicon layer 206 is formed by forming an interconnectedporous structure in the amorphous silicon layer. In one embodiment,anodization techniques are used to form the interconnected porousstructure in the amorphous silicon layer. The anodization techniquescomprise immersing the current collector in an electrolytic solution.The electrolytic solution may be any acidic solution. Suitable acidsolutions include, for example, inorganic acids such as sulfuric acid,phosphoric acid, pyrophosphoric acid, perchloric acid, acetic acid,citric acid, combinations thereof, as well as acid electrolytederivatives, including ammonium and potassium salts thereof. In oneembodiment, the electrolytic solution comprises a combination of 50%hydrofluoric acid and 50% acetic acid. Optionally, the electrolyticsolution may include one or more additive compounds.

The interconnected pores are formed by passing a direct current throughthe electrolytic solution, with a metal electrode serving as the anode(the positive electrode) and the current collector 111 with theamorphous silicon layer 204 deposited thereon serving as the cathode(negative electrode). The current releases hydrogen at the cathode (thenegative electrode) and oxygen at the surface of the anode. In oneembodiment, alternating current may be used. In one embodiment, pulsedcurrent may be used. The voltage required by various solutions may rangefrom about 1 Volt to about 300 Volts DC. The anodizing current varieswith the area of the current collector. In one embodiment, the anodizingcurrent ranges from about 20 mA/cm² to about 100 mA/cm². In oneembodiment the anodizing current ranges from about 50 mA/cm² to about 80mA/cm². Conditions such as electrolyte concentration, acidity, solutiontemperature, and current may be varied to allow the formation ofinterconnected pores of varying sizes.

With reference to FIG. 3, the diameter of each of the interconnectedpores 306 may be controlled by varying the voltage applied during theanodization process since pore diameter is proportions to the voltageapplied. In one embodiment, a first voltage range is applied to form thefirst set of pores 312 having the first diameter 314 extending from thetop surface 308. In one embodiment, the first voltage range is decreasedto a second voltage range. As the first voltage range is decreased tothe second voltage range, the first set of pores 312 splits intomultiple pores 318 a, 318 b, 318 c having a second diameter 320 lessthan the first diameter. In one embodiment, the second voltage range isdecreased to a third voltage range. As the second voltage range isdecreased to the third voltage range, each of the multiple pores 318 a,318 b, 318 c splits into multiple pores 326 a, 326 b, 326 c having athird diameter 328 less than the second diameter 320. In one embodiment,after formation of the first pore 312 sequential reduction of theanodization voltage allows for further branching of the interconnectedpores. In one embodiment, if the voltage is reduced gradually, the firstpores divide gradually but if the voltage is decreased sharply, thefirst pores divide abruptly. In one embodiment, the anodization voltagefor formation of the first pores 312 is between about 40 volts and about100 volts. In one embodiment, the anodization voltage may be reduced bya factor of 1/√n where n is the number of branches formed. For example,reduction of the anodization voltage by a factor of 1/√3 may be used forformation of multiple pores 318 a, 318 b, 318 c.

The density, diameter, and alignment of the interconnected pores arecontrolled so that the density, diameter, and alignment of the graphiticnanofilaments may also be controlled. The interconnected pore density isthe number of pores per unit area of the top surface of the porousamorphous silicon layer. In one embodiment, the interconnected pores maybe aligned as desired relative to the top surface of the porousamorphous silicon layer.

In one embodiment, an endpoint for the anodization process is reachedwhen the current collector 111 is exposed causing the current to spike.In embodiments where the interconnected pores are not through pores, thecurrent spike may also be used to detect an endpoint prior to exposureof the underlying current collector 111 for the anodization process

At block 608, graphitic nanofilaments such as carbon nanotubes or carbonnanofibers are formed inside the pores of the porous amorphous siliconstructure. One desirable processing technique that can be used to formthe carbon nanotubes is a chemical vapor deposition process (CVD). Thechemical vapor deposition (CVD) techniques used to form carbon nanotubesmay be generally categorized into two types: catalytic andnon-catalytic. The methods which use catalyst materials to facilitateand help control the growth of carbon nanotubes are referred to ascatalytic CVD methods. The methods which use no catalyst materials forcarbon nanotube growth are referred to as non-catalytic or pyrolytic CVDmethods since only heating, and not catalysis, typically drivesnanofilament growth. The catalytic CVD methods often provide greatercontrol over carbon nanotube growth than non-catalytic methods. Variousmethods of carbon nanotube growth are described by K. Teo et al., in“Catalytic Synthesis of Carbon Nanotubes and Nanofibers,” Encyclopediaof Nanoscience and Nanotechnology, Volume X, pg. 1-22, AmericanScientific Publishers, 2003.

The graphitic nanofilament type (nanotube or nanofiber), structure(single-walled, multi-walled, herringbone, etc.), diameter, length andalignment may be controlled by controlling the CVD growth parameters.The growth parameters include but are not limited to carbon source gas,carrier gas, growth temperature, growth pressure, and growth time. Forcatalytic CVD growth, additional growth parameters may include catalystparameters such as catalyst size, shape, composition, and catalystprecursors. The parameter ranges and options for catalytic CVD growth,excluding catalyst parameters, may, in general, be applicable to thenon-catalytic CVD growth of graphitic nanofilaments, although highertemperatures may be used for the non-catalytic CVD methods.

Generally, the temperatures for the catalytic CVD growth of graphiticnanofilaments may range from about 300 degrees Celsius (° C.) to about3000 degrees Celsius (° C.). In one embodiment, the temperatures for thecatalytic CVD growth may range from about 600° C. to about 1200° C.,although temperatures lower than 600° C. may be used, especially if theCVD growth is plasma enhanced. The growth pressures may range from about0.1 Torr to about 1 atmosphere, but more preferably from about 0.1 Torrto about 100 Torr, although lower or higher pressures may also be used.In another embodiment, the growth pressures are above atmosphericpressure, and may range from about 1 atmosphere to about 10 atmospheres.The growth time or “residence time” depends in part on the desiredgraphitic nanofilament length, with longer growth times producing longerlengths. The growth time may range from about ten seconds to many hours,but more typically from about ten minutes to several hours. In oneembodiment, the growth time is in a range between about 1 minute andabout 5 minutes.

The carbon source gas used for graphitic nanofilament growth may includebut is not limited to ethylene, propylene, acetylene, benzene, toluene,ethane, methane, butane, propane, hexane, methanol, ethanol, propanol,isopropanol, carbon monoxide, acetone, oxygenated hydrocarbons,low-molecular-weight hydrocarbons, high-molecular weight hydrocarbons orcombinations thereof. In general, the carbon source gas may comprise anycarbon-containing gas or gases, and the carbon source gas may beobtained from liquid or solid precursors for the carbon-containing gasor gases. An auxiliary gas may be used with the carbon source gas tofacilitate the growth process. The auxiliary gas may comprise one ormore gases, such as carrier gases, inert gases, reducing gases (e.g.,hydrogen, ammonia), dilution gases, or combinations thereof, forexample. The term “carrier gas” is sometimes used in the art to denoteinert gases, reducing gases, and combinations thereof. Some examples ofcarrier gases are hydrogen, nitrogen, argon, and ammonia.

Suitable catalyst materials may include but are not limited to iron,cobalt, nickel, copper, silver, magnesium, ruthenium, rhodium, iridium,platinum, palladium, molybdenum, tungsten, chromium and alloys, oxides,and combinations thereof. Combinations or mixtures of catalyst materialswhich may be used include but are not limited to iron-nickel,iron-molybdenum, iron-cobalt, cobalt-nickel, and cobalt-molybdenum.Preferred catalysts include iron, cobalt, nickel and alloys thereof.

The graphitic nanofilaments are grown within the interconnected poresand the density, diameter, and alignment of the nanofilaments mayclosely reproduce the density, diameter, and alignment of theinterconnected pores. Catalyst particles may be deposited within theinterconnected pores 208 to enable catalytic nanofilament growth (eitherbase-growth or tip-growth). Alternately, the growth of the graphiticnanofilaments within the nanopores may be non-catalytic (i.e.,pyrolytic).

FIGS. 7A-7G are schematic cross-sectional views of one embodiment of ahigh surface area electrode formed in accordance with embodimentsdescribed herein. FIG. 8 is a process flow chart 800 summarizing oneembodiment of a method for forming a high surface area electrodeaccording to embodiments described herein. The sequence found in FIG. 8corresponds to the stages depicted in FIGS. 7A-7G, which are discussedherein. The composite materials may be formed on discrete substrates Sas shown in FIG. 7A or on a web in a roll-to-roll process. Such asubstrate S is shown in FIG. 7A. The substrate S can be made of, but isnot limited to: glass, silicon (Si) or metal such as aluminum (Al),stainless steel, or copper (Cu). In one embodiment, the substrate S maybe relatively non-flexible when provided as a discrete substrate, butrelatively flexible when supplied as a web (for example, aluminum,stainless steel, or copper foil). In another embodiment, the substratemay be flexible when provided as a discrete substrate.

At block 802, as shown in FIG. 7A, a substrate S is positioned in aprocessing region and a layer 702 of catalytic material is deposited onthe substrate S. In one embodiment, the catalytic material of layer 702comprises: iron (Fe); cobalt (Co); nickel (Ni); alloys thereof, polymersthereof, and combinations thereof. In one embodiment, the layer ofcatalytic material 702 may be deposited on the substrate S using anumber of methods including a physical vapor deposition (PVD) methodsuch as sputtering, or a chemical vapor deposition (CVD) method, asdescribed above. In one embodiment, the layer of catalytic material 702is deposited to a thickness of about 0.2 nm to about 20 nm. In oneembodiment, the layer of catalytic material 702 is deposited to athickness of less than about 20 nm.

Next, during block 804, as illustrated in FIG. 7C, the depositedcatalyst material 702 is further processed to form nanoislands 704 ofcatalyst material on the substrate S. In one embodiment, the processingstep(s) used to form the nanoislands 704 includes heating the substrateS to a desired temperature for a desired period of time. In oneembodiment, the temperature in the processing region may be constant ormay be increased over time. In one embodiment, the temperatures in theprocessing region for forming the nanoislands may be between about 300°C. and about 1,000° C. In one embodiment, the temperatures in theprocessing region for forming the nanoislands may be between about 500°C. and about 800° C.

Next, during block 806, as illustrated in FIG. 7D, graphiticnanofilaments 706 are formed on the substrate S. By supplying a carboncontaining precursor to the surface of the substrate S that contains thenanoislands 704, graphitic nanofilaments 706 can be formed on a surfaceof the substrate S. In one embodiment, the graphitic nanofilaments 706comprise carbon nanotubes or nanofibers that are single-walled ormulti-walled as described above. In one embodiment, the carboncontaining precursor is selected from a group of carbon source gasescomprising: xylene, ethylene, propylene, acetylene, benzene, toluene,ethane, methane, butane, propane, hexane, methanol, ethanol, propanol,isopropanol, carbon monoxide, acetone, oxygenated hydrocarbons,low-molecular-weight hydrocarbons, and combinations thereof. In someembodiments, the process to form the nanotubes may be a plasma enhancedchemical vapor deposition (PECVD) process. In further embodiments, theprocess to form the nanotubes 706 may be a hot-wire chemical vapordeposition process (HWCVD) or an iCVD process.

Next, during block 808, as illustrated in FIG. 7E, a silicon containinglayer 708 is deposited over the graphitic nanofilaments 706 formedduring block 806. In one embodiment, the silicon containing layer is anamorphous silicon layer that is between about 0.5 nm and about 10 nmthick. In one embodiment, an amorphous silicon layer is formed over thegraphitic nanofilaments 706 using a HWCVD process. The HWCVD processgenerally uses a hot filament (usually tungsten or tantalum) to “crack”the reactive gas components (e.g., silane and hydrogen) into atomicradicals. The hot filament is typically maintained at a surfacetemperature grater than 1500° C. The reactive species, after passingacross the surface of the hot filament, are transported through aprocessing region to the substrate in a low pressure ambient whichenables a high deposition rate without gas-phase particle formation. Inone embodiment, as shown in FIG. 7E, an amorphous silicon layer 708 isdeposited and conformably coats the graphitic nanofilaments 706.Silicon-containing gases for forming the amorphous silicon layer on thegraphitic nanofilaments include, for example, hydrogen (H₂), silane(SiH₄), disilane (Si₂H₆), silicon tetrafluoride (SiF₄), silicontetrachloride (SiCl₄), dichlorosilane (SiH₂Cl₂), and combinationsthereof.

Next, during block 810, as illustrated in FIG. 7F, a polymeric layer isdeposited over the silicon containing layer formed during block 808. Inone embodiment, after the amorphous silicon 708 is deposited on thesurface of the substrate, a polymeric material 710, such as apolytetrafluoroethylene (PTFE), is deposited thereon. The polymericmaterial 710 is generally used to provide a dielectric barrier and/orencapsulate both the graphitic nanofilaments 706 and the amorphoussilicon layer 708. In one embodiment, the formed layer of polymericmaterial 710 is porous. In one embodiment, the polymeric material 710 isdeposited on the amorphous silicon 708 and graphitic nanofilaments 706using an initiated chemical vapor deposition (iCVD) process. The iCVDprocess generally involves the vapor phase delivery of both initiatorspecies and monomers into a processing region that is maintained in avacuum state. In one embodiment, the iCVD process is performed at usinga low temperature between about 300° C. and 450° C., such as about 400°C.

During block 812, as illustrated in FIG. 7G a cathodic layer 712 ofmaterial is deposited on top of the polymeric material 710, to form acathode and complete the composite material structure. In oneembodiment, the cathodic layer 712 is a lithium (Li) based material,such as lithium transition metal oxides, such as LiMn₂O₄, LiCoO₂, and/orcombinations of Ni and Li oxides. In one embodiment, the cathodicmaterial includes a series of layers which include a lithium containinglayer and a metal layer. In one example, the metal layer includes but isnot limited to include aluminum, stainless steel, and nickel. Thecathodic material may be deposited using at least one of a PVD, PECVD,CVD, iCVD, or HWCVD process.

FIGS. 9A-9D are schematic isometric views of one embodiment of a highsurface area electrode formed in accordance with embodiments describedherein. FIG. 10 is a process flow chart 1000 summarizing one embodimentof a method for forming a high surface area electrode according toembodiments described herein. The process sequence found in FIG. 10corresponds to the schematic isometric views of FIGS. 9A-9D. Thecomposite materials may be formed on discrete substrates S as shown inFIG. 9A or on a web in a roll-to-roll process. Such a substrate S isshown in FIG. 9A. The substrate S can be made of, but is not limited to:glass, silicon (Si) or metal such as aluminum (Al), stainless steel, orcopper (Cu). In one embodiment, the substrate S may be relativelynon-flexible when provided as a discrete substrate, but relativelyflexible when supplied as a web (for example, aluminum, stainless steel,or copper foil). In another embodiment, the substrate may be flexiblewhen provided as a discrete substrate.

At block 1002, as shown in FIG. 9B, a substrate S is positioned in achamber and a layer 902 of a silicon (Si) matrix 904 with an Aluminum(Al) phase 906 segregated therein is deposited on the substrate S. Inone embodiment, the layer 902 is deposited using a PVD sputteringprocess. In one embodiment, a target of Al₅₆Si₄₄ is positioned in aprocessing region. A power source is connected to the target so that acathodic DC and/or RF bias can be applied to the target so that thelayer 902 can be deposited on the surface of the substrate S. The plasmagenerated by the bias applied to the target causes atoms from the targetsurface to be removed, and be deposited on the exposed surfaces of thesubstrate S. In one embodiment, the power supplied by the power sourceis between about 100 W and about 200 W. In one embodiment, the substrateS may be heated to a substrate temperature of between about 50° C. andabout 500° C. In one embodiment the substrate S is heated to a substratetemperature between about 100° C. and about 200° C. In anotherembodiment, the substrate S is heated to a temperature less than 150° C.As layer 902 is sputtered onto the substrate S, the aluminum phase 906is segregated in the silicon matrix 904.

After the formation of layer 902 on the substrate S, process 1000proceeds to block 1004. In block 1004, the aluminum is etched out of thesilicon matrix. In one embodiment, the etching of the aluminum isperformed using a wet etch process. After the aluminum has been etchedout of the silicon matrix, the resulting structure is as is shown inFIG. 9C. The substrate S includes a porous silicon layer 908 disposedthereon. The porous silicon layer 908 is formed by removing the aluminumphase 906 from the silicon matrix 904 to form a plurality of pores 910.The distance between the plurality of pores 910 can be tuned

Next, during block 1006, as illustrated in FIG. 9D, carbon nanotubes(CNT) 912 are deposited in the pores 910 of the porous silicon layer908. In one embodiment, the CNTs 912 are formed in the porous siliconlayer 908 using a CVD process. The CNTs 912 can be grown in the poroussilicon layer 908 by first depositing and heating catalyst material toform nanoislands of catalyst material in the pores 910 of the poroussilicon layer 908. The gasses for forming the catalyst material on thesubstrate and the gasses for forming the CNTs may be sequentiallysupplied, or may be simultaneously provided (co-flowed). By firstproviding the gasses required to form the catalyst, then heating thecatalyst to form the nanoislands, and following with the gasses to formthe CNTs, CNTs that are relatively free of catalyst particles can beformed. When the gasses for forming the catalyst and the CNTs aresimultaneously provided, some amount of catalyst particles may bepresent on the resulting CNTs. In some applications, a small amount ofcontamination is acceptable. Thus, the increased substrate throughput ofa co-flowed method may be desirable. The CNTs may be formed using any ofthe processes described herein as well as other known processes. TheCNTs provide excellent electrical conductivity for electrons as well assupporting the structural integrity of the structure.

After the deposition of CNTs in the silicon matrix, in some embodiments,additional silicon is deposited at block 1008 of process 1000, on thestructure shown in FIG. 9D. The additional Si may be deposited usingHWCVD or other suitable processes. In one embodiment, the siliconcontaining layer is an amorphous silicon layer that is between about 10nm and about 1,000 nm thick. Referring to FIG. 11, a chamber isconfigured and adapted to deposit the amorphous silicon on the Si/CNTmatrix (904 and 912 of FIG. 9D) using a HWCVD process.Silicon-containing gases for forming the amorphous silicon layer on thegraphitic nanofilaments include, for example, hydrogen (H₂), silane(SiH₄), disilane (Si₂H₆), silicon tetrafluoride (SiF₄), silicontetrachloride (SiCl₄), dichlorosilane (SiH₂Cl₂), and combinationsthereof.

The structure shown in FIG. 9D is advantageously used in the formationof an electrode structure for energy storage devices. The Si-CNTnanocomposite formed by depositing a plurality of nanotubes 912 in thepores 910 of the silicon matrix 904 provides several advantages. Onesuch advantage is that the partial exposure of the porous silicon allowsfor higher current capacity in excess of 3400 mAh/g. Another advantageis the ability of the structure to accommodate volume expansion (such asthermal expansion) through the presence of the pores 910. In addition,the nature of the CNTs when incorporated in the inventive structureprovide for prolonged cycle life, excellent structural integrity, andexcellent electronic conduction pathways. The scalability of thesenanostructures will also reduce costs of the final products in bothelectric vehicle (EV) and consumer electronic markets.

FIG. 11 is a schematic plan view of one embodiment of a processingsystem (e.g., cluster tool 1100) that may be used to form the highsurface area electrodes discussed herein. The cluster tool 1100 includesa vacuum-tight processing platform 1101, a factory interface 1102, and asystem controller 1136. The platform 1101 comprises a plurality ofprocessing modules 1108, 1110, 1112, 1114, 1116, 1118, 1124 and at leastone load-lock chamber (a load-lock chamber 1120 is shown), which arecoupled to vacuum substrate transfer chambers 1103, 1104. The factoryinterface 1102 is coupled to the transfer chamber 1104 by the load lockchamber 1120.

In one embodiment, the factory interface 1102 comprises at least onedocking station 1126, at least one substrate transfer robot 1138, atleast one substrate transfer platform 1140, at least one precleaningchamber 1124, and a precleaning robot 1122. In one embodiment, thedocking station 1126 is configured to accept at least one front openingunified pod (FOUP). Two FOUPs 1128A, 1128B are shown in the embodimentof FIG. 11, but any number of FOUPs may be provided within the physicallimits of the docking station 1126. The substrate transfer robot 1138 isconfigured to transfer the substrate from the factory interface 1102 tothe precleaning chamber 1124 wherein a precleaning process may beperformed. The precleaning robot 1122 is configured to transfer thesubstrate from the precleaning chamber 1124 to the loadlock chamber1120. Alternatively, the substrate may be transferred from the factoryinterface 1102 directly to the loadlock chamber 1120, by-passing theprecleaning chamber 1124.

The loadlock chamber 1120 has a first port coupled to the factoryinterface 1102 and a second port coupled to a first transfer chamber1104. The loadlock chamber 1120 is coupled to a pressure control system(not shown) which pumps down and vents the chamber 1120 as needed tofacilitate passing the substrate between the vacuum environment of thetransfer chamber 1104 and the substantially ambient (e.g., atmospheric)environment of the factory interface 1102.

The first transfer chamber 1104 has a first robot 1107 disposed therein.The first robot 1107 transfers substrates between the loadlock chamber1120, the processing modules 1116 and 1118 , and two substrate transferplatforms 1106A and 1106B. The second transfer chamber 1103 has a secondrobot 1105 disposed therein. The second robot 1105 transfers substratesbetween the two substrate transfer platforms 1106A and 1106B and theprocessing modules 1108, 1110, 1112 and 1114. The two substrate transferplatforms 1106A, 1106B are disposed between the transfer chamber 1104and the transfer chamber 1103 to facilitate transfer of the substratebetween the robot 1105 and the robot 1107. The platforms 1106A, 1106Bcan either be open to the transfer chambers 1103, 1104 or be selectivelyisolated (i.e., sealed) from the transfer chambers 1103, 1104 to allowdifferent operational pressures to be maintained in each of the transferchambers 1103, 1104.

In one embodiment, the processing chambers coupled to the first transferchamber 1104 may be a third hot-wire CVD (HWCVD) chamber 1118, aphysical vapor deposition (PVD) or chemical vapor deposition (CVD)chamber 1116, for performing a CVD process such as hot-wire CVD (HWCVD).The processing chambers coupled to the second transfer chamber 1103 maybe a first PVD chamber 1112, a second PVD chamber 1114, a first HWCVDchamber 1110, and a second HWCVD chamber 1108. Suitable CVD, PVD, HWCVDand degas processing chambers are available from Applied Materials,Inc., located in Santa Clara, Calif.

The system controller 1136, used to control the various components inthe tool 1100, generally has a memory 1113, a central processing unit(CPU) 1109 and support circuits 1111. The system controller 1136 isutilized to control the process sequence of the chambers, regulating thegas flows from gas sources and power application from power sources intothe chambers. The system controller 1136 is coupled to the integratedprocessing tool 1100. The system controller 1136 controls the operationof the tool 1100 using a direct control of the process chambers of thetool 1100 or alternatively, by controlling the computers (orcontrollers) associated with the process chambers and tool 1100. Inoperation, the system controller 1136 enables data collection andfeedback from the respective chambers and system to optimize performanceof the tool 1100.

FIG. 12 is a schematic side view of one embodiment of an apparatus 1200for forming a high surface area electrode on substrates in the form of aweb, showing the various chambers for forming the high surface areaelectrode. The substrate in FIG. 12 is in the form of a continuous web1201 of material. The apparatus 1200 includes various chambers 1202,1204, 1206, and 1208 for forming the high surface area electrodes. Theapparatus 1200 has a first end 1214 where a supply roll 1218 stores theunprocessed substrate(s), web 1201, and feeds the web 1201 into thefirst chamber 1202. The apparatus 1200 has a second end 1216 where atake-up roll 1230 receives and stores the processed substrate(s), web1203, with the high surface area electrode materials deposited thereon.At the first end 1214 a first diverter roller 1220 receives web 1201from the supply roll 1218, and diverts the web 1201 into the firstchamber 1202. At the second end 1216, a second diverter roller 1222receives the processed web 1203 from the final chamber 1208 and divertsit to the take-up roll 1230. In some embodiments, a roll 1232 of aprotective web of material 1234 may be routed unto take-up roll 1230.The web of protective material 1234 isolates adjacent layers ofprocessed web 1203, to thereby protect the web 1203 while it is storedand or transported on roll 1230.

A series of substrate transfer ports 1224 are provided at the entranceand exit of the apparatus 1200 and between each of the chambers 1202,1204, 1206, and 1208 to allow the substrates to pass between chambers,while maintaining the required environment within each chamber duringprocessing. A series of rollers 1226 supports the web 1201 of materialas it is guided through the various chambers. In some embodiments, adrive belt (not shown) may be included to form a conveyor to provideadditional support to the web 1201 between the rollers 1226. The rollers1226 may be mechanically driven by a common drive system (not shown)such that they are controlled in unison, thereby avoiding wrinkling orstretching of the web 1201. The rollers 1226 may advance the web 1201into the subsequent chambers, based on commands received by a drivemechanism 1314 (FIG. 13) from the support circuits 1211 (FIG. 12) of thesystem controller 1205. While in the embodiment of FIG. 12, fourchambers are shown, more or less chambers may be provided depending onthe number of processes and the required equipment for each process. Inone embodiment, the apparatus 1200 also contains at least one additionalchamber (not shown) at either end 1214, 1216 of the system that act as aload lock to provide a buffer between the environment external to theapparatus 1200 and the processing regions of the chambers 1202-1208. Thevarious drives for the supply roll 1218, take-up roll 1230, rollers1226, ports 1224 and other system actuators are provided control signalsfrom a system controller 1205. The controller 1205 has a memory 1207, acentral processing unit (CPU) 1209 and support circuits 1211 that arecoupled to the apparatus 1200. The controller 1205 is utilized tocontrol the process sequence of the chambers, regulating the gas flowsfrom gas sources and power application from power sources into thechambers. The CPU 1209 may be of any form of a general purpose computerprocessor that can be used in an industrial setting. The softwareroutines can be stored in the memory 1207, such as random access memory,read only memory, floppy or hard disk drive, or other form of digitalstorage. The support circuits 1211 are conventionally coupled to the CPU1209 and may comprise cache, clock circuits, input/output subsystems,power supplies, and the like. The software routines, when executed bythe CPU 1209, transform the CPU into a specific purpose computer(controller) 1205 that controls the process chambers such that theprocesses are performed in accordance with the present invention. Thesoftware routines may also be stored and/or executed by a secondcontroller (not shown) that is located remotely from the apparatus 1200.

FIG. 13 is a schematic side view of one embodiment of a chamber 1202 fordepositing silicon on a substrate. During block 604, as illustrated inFIGS. 2B and 13, a silicon containing layer is deposited over the web1201. In one embodiment, the silicon containing layer is an amorphoussilicon layer that is between about 100 nm and about 3 μm thick.Although FIG. 2 shows current collector 111 as a discrete substrate, itshould be understood that in certain embodiment, current collector 111may be replaced by a web such as web 1201. In one embodiment, theamorphous silicon layer is formed over the web 1201 using a hot wirechemical vapor deposition (HWCVD) process. In one embodiment, as shownin FIG. 13, a chamber 1202 is configured and adapted to deposit theamorphous silicon on the web 1201 using a HWCVD process. The HWCVDprocess generally uses a hot filament (usually tungsten or tantalum) to“crack” the reactive gas components (e.g., silane and hydrogen) intoatomic radicals. The hot filament is typically maintained at a surfacetemperature significantly higher than 1500° C. The reactive species,after passing across the surface of the hot filament, are transportedthrough a processing region 1352 to the substrate in a low pressureambient which enables a high deposition rate without gas-phase particleformation. In one example, an amorphous silicon layer 204 is depositedand coats the conductive web 1201. To accomplish this, the chamber 1202includes a showerhead 1316 that receives process gasses from one or moregas sources 1318, 1320 via valves 1322, 1324, respectively. In oneembodiment, the one or more gas sources comprise a silicon containinggas source. The valves 1322, 1324 are controlled by signals receivedfrom the support circuits 1211 of the system controller 1205. The gassessupplied by the shower head 1316, for forming amorphous silicon on theweb 1201 include, for example, hydrogen (H₂), and silicon containinggases, such as silane (SiH₄), disilane (Si₂H₆), silicon tetrafluoride(SiF₄), silicon tetrachloride (SiCl₄), and/or dichlorosilane (SiH₂Cl₂).To assist in the CVD process, a resistive wire 1328 is placed in closeproximity to the web 1201. Electrical current is supplied to the wire1328 by a power supply 1326, based on signals received from the supportcircuits 1211 of the system controller 1205. The electrical currentheats the wire 1328 to form the amorphous silicon 204 on the conductiveweb 1201. In embodiments requiring heating of the web 1201, one or moreheating elements 1212 may be provided.

In this embodiment, the chamber 1202 includes a first wall 1340 facingthe first end 1214 of apparatus 1200 and a second wall 1340′ betweenchamber 1202 and chamber 1204. While second wall 1340′ is shown as ashared wall between chambers 1202 and 1204, double walls may be used ifrequired (e.g., to provide greater insulation between chambers). Thechamber 1202 also includes a top 1302, that may be a common one-piecetop for all of the chambers as shown, or each chamber could be providedwith a separate top. As with the top 1302, chamber bottom 1304 may be acommon one-piece bottom for all of the chambers as shown, or eachchamber could be provided with a separate bottom.

In one embodiment, a pumping device 1330 is coupled to the processingregion 1352 to evacuate and control the pressure therein. The pumpingdevice 1330 may be a conventional rough pump, roots blower, turbo pumpor other similar device that is adapted control the pressure in theprocessing region 1352. In one embodiment, the pressure level of theprocessing region 1352 of the chamber 1202 may be maintained at lessthan about 760 Torr. In one embodiment, the pressure level of theprocessing region 1352 of the chamber 1202 may be maintained at about 1Torr or less. In another embodiment, the pressure level within thechamber 1202 may be maintained at about 10⁻³ Torr or less. In yetanother embodiment, the pressure level within the chamber 1202 may bemaintained at about 10⁻³ Torr to about 10⁻⁷ Torr.

FIG. 14 is a schematic side view of one embodiment of an anodizationchamber 1204 for performing an anodization process on a substrate.During block 606, as illustrated in FIGS. 2C and 13, an interconnectedporous silicon structure 206 is formed. The anodization chamber 1204 isconfigured to form pores in the amorphous silicon layer 204. Theanodization chamber 1204 generally comprises a chamber body 1403defining a processing volume 1404. The processing volume 1404 is influid communication with one or more inlet jets 1405 configured todispense an anodization solution in the processing volume 1404. Theprocessing volume 1404 is also in fluid communication with a drain 1406configured to remove the plating solution from the processing volume1404.

The anodization chamber 1204 also comprises an anode assembly 1420disposed in the processing volume 1404. In one embodiment, the anodeassembly 1420 is disposed in a substantially vertical orientation. Inone embodiment, the anode assembly 1420 may contain a plurality of holes1418 that allow the anodization bath passing from the inlet jets 1405 tohave a uniform flow distributed across a surface of the web 1201.

The anode assembly 1420 may be formed from material that is consumableduring the electroplating reaction, but is more preferably formed from anon-consumable material. A non-consumable electrode may be made of aconductive material that is not etched during the process, such asplatinum or ruthenium coated titanium. In one embodiment, the anodeassembly 1420 is horizontally movable.

In one embodiment, the anodization chamber 1204 comprises a thrust plate1430 disposed in the processing volume 1404, substantially parallel tothe anode assembly 1420. The thrust plate 1430 is configured to hold aportion of the web 1201 in a position relative to the anode assembly1420 during the anodization process. The thrust plate 1430 is positionedon a backside of the web 1201 and the anode assembly 1420 is positionedon a front side of the flexible web 1201.

In one embodiment, the thrust plate 1430 is horizontally movable. Duringtransferring stage, the thrust plate 1430 is moved away from theflexible web 1201 and neither the anode assembly 1420 nor the thrustplate 1430 is in contact with the flexible web 1201. Before processing,at least one of the thrust plate 1430 and the anode assembly 1420 ismoved towards the other sandwiching the flexible web 1201 in between.The thrust plate 1430 ensures that the flexible web 1201 issubstantially parallel to the anode assembly 1420 and in a desireddistance from the anode assembly 1420. A power source 1417 is coupledbetween the anode assembly 1420 and a cathode assembly 1407 to provideelectric bias for anodization process.

FIG. 15A is a schematic side view of one embodiment of a chamber 1206for depositing catalyst material on a substrate. During block 608, anoptional layer of catalytic material is deposited over the porousamorphous silicon structure prior to the formation of carbon nanotubesinside pores of the porous amorphous silicon structure. The catalyticmaterial can be formed of, but is not limited to iron (Fe); cobalt (Co);nickel (Ni); alloys of Fe, Co and Ni; Fe polymer; Co polymer; and Nipolymer. The layer of catalytic material may be deposited on thesubstrate S using a number of methods including a physical vapordeposition (PVD) method such as sputtering, or a chemical vapordeposition (CVD) method.

In one embodiment, a chamber 1206 of FIG. 15A, is configured and adaptedto deposit the catalyst material using a sputtering deposition process.A target 1508 of the catalyst material is provided in the chamber 1206.A power source 1510 is connected to the target 1508 so that a cathodicDC and/or RF bias can be applied to the target 1508 so that thecatalytic material can be deposited over the web 1201. The plasmagenerated by the bias applied to the target 1508 causes atoms from thetarget surface to be removed, and deposited inside the pores of theinterconnected porous amorphous silicon structure. In embodimentsrequiring heating of the substrates, one or more heating elements 1212may be provided. The heating elements 1212 may comprise resistiveheating elements, induction coils, or other heating means.

FIG. 15B is a schematic side view of another embodiment of a chamber1206′ for depositing catalyst material on a substrate. In anotherembodiment, a chamber 1206′ of FIG. 15B is used to deposit catalystmaterial on the substrates S positioned in a processing region 1548using a chemical vapor deposition (CVD) process. One will note that thecomponents found in chamber 1206′ (and the other chambers as describedbelow) are generally similar to the components founds in chamber 1202 inFIG. 13, and thus have the same reference designators, and are notdescribed with reference to FIG. 15B. In chamber 1206′, process gassesare provided to a showerhead 1516 from one or more gas sources 1518,1520 via valves 1522, 1524, respectively. Valves 1522, 1524 arecontrolled by signals received from the support circuits 1211 of thesystem controller 1205. The process gasses provided to the showerhead1516 include gasses used to form the catalytic material, such as metalorganic precursors. While in this embodiment, two gas sources 1518, 1520are shown, a single gas source or a plurality of gas sources may beprovided depending on the number and combination of gases used. Toimprove the film quality, increase the deposition rate and/or filmuniformity, the CVD process may be enhanced by applying a bias to theshowerhead 1516 and/or the web 1201. In one embodiment, a power supply1526 is configured to RF bias the showerhead 1516 based on signalsreceived from the support circuits 1211 of the system controller 1205.The applied voltage may be RF, DC or AC depending on systemrequirements. In another embodiment, an inductively coupled plasma mayalso be formed in the processing region 1548 by use of the power supply1526 and

FIG. 16 is a schematic side view of one embodiment of a chamber 1208 fordepositing carbon nanotubes on a substrate positioned in a processingregion 1554. During block 608, as illustrated in FIG. 2D carbonnanotubes are formed inside the pores of the porous amorphous siliconstructure. In one embodiment, the carbon nanotubes are formed in thepores of the porous amorphous silicon structure using a hot wirechemical vapor deposition (HWCVD) process. In one embodiment, as shownin FIG. 16, the chamber 1208 is configured and adapted to deposit thecarbon nanotubes on the substrate using a HWCVD process as describedabove. To accomplish this, the chamber 1208 includes a showerhead 1616that receives process gasses from one or more gas sources 1618, 1620 viavalves 1622, 1624, respectively. In one embodiment, the one or more gassources comprise a carbon containing source gas. The valves 1622, 1624are controlled by signals received from the support circuits 1211 of thesystem controller 1205. To assist in the CVD process, a resistive wire1628 is placed in close proximity to the web 1201. Electrical current issupplied to the wire 1628 by a power supply 1626, based on signalsreceived from the support circuits 1211 of the system controller 1205.The electrical current heats the wire 1628 to form the carbon nanotubesinside the pores of the porous amorphous silicon structure.

EXAMPLES

The following hypothetical non-limiting examples are provided to furtherillustrate embodiments described herein. However, the examples are notintended to be all inclusive and are not intended to limit the scope ofthe embodiments described herein.

Porous Si-CNT on a 300 mm Substrate:

With reference to FIG. 11 and FIGS. 9A-9D, the substrate S istransferred into the integrated processing tool 1100. The substrate istransferred into the first PVD chamber 1112 where copper is deposited onthe substrate S using a PVD sputtering process. The substrate S istransferred to the second PVD chamber 1114 where the silicon (Si) matrix904 with an aluminum (Al) phase 906 segregated therein is deposited onthe substrate S as shown in FIG. 9B. Next, the substrate S istransferred to a wet etch chamber where the aluminum phase 906 isremoved from the silicon matrix 904 using a wet etch process. The wetetch may be performed either in a dedicated wet etch chamber coupledwith the integrated processing tool 1100 or the wet etch may beperformed in a remote chamber. As shown in FIG. 9C, a plurality of pores910 are formed after the aluminum has been etched out of the siliconmatrix. The substrate S is transferred into the first HWCVD chamber 1110where CNTs 912 are formed in the plurality of pores 910 as shown in FIG.9D. After formation of the CNTs 912 the substrate S is transferred tothe second HWCVD chamber 1108 where additional silicon is deposited onthe structure shown in FIG. 9D.

Nanostructured Si-CNT on a 300 mm Substrate:

With reference to FIG. 11 and FIGS. 7D-7E, a substrate S is transferredinto the integrated processing tool 1100. The substrate is transferredinto the CVD chamber 1116 where a catalyst is deposited on the substrateS using a vapor phase CVD process. The substrate S is transferred intothe first HWCVD chamber 1110 where CNTs 706 are formed on the substrateS. After formation of the CNTs 706 the substrate S is transferred to thesecond HWCVD chamber 1108 where additional silicon 708 is deposited onthe structure as shown in FIG. 7E. Next, the substrate may betransferred to the third HWCVD chamber 1118 where a polymeric material710 is deposited over the substrate S.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

1. An apparatus for forming an energy storage device on a substratecomprising at least one continuous web of conductive material,comprising: a first end; a second end; a support system to support theat least one continuous web of conductive material extending from thefirst end to the second end; a first chamber disposed between the firstand the second end for depositing an amorphous silicon layer on the atleast one continuous web of conductive material, wherein the firstchamber comprises: a hot filament adapted to be heated at a surfacetemperature higher than 1,500° C.; a showerhead that is adapted todeliver a silicon containing gas to form the amorphous silicon layer onthe at least one continuous web of conductive material using a hot wirechemical vapor deposition (HWCVD) process; and a silicon containing gassource coupled with the showerhead for delivery of the siliconcontaining gas to the showerhead; and a second chamber disposed betweenthe first end and the second end for exposing the amorphous siliconlayer to an anodization process, wherein the second chamber, comprises:a processing volume adapted to hold an electrolytic solution; an anodeassembly disposed in the electrolytic solution, wherein the anodeassembly is movable to contact the substrate and anodically bias thesubstrate; a cathode assembly disposed in the electrolytic solution; oneor more inlet jets configured to dispense the electrolytic solution intothe processing volume; and a power supply adapted to deliver power tothe anode assembly and the cathode assembly such that the amorphoussilicon layer is anodized to form an interconnected porous amorphoussilicon layer.
 2. The apparatus of claim 1, further comprising: a thirdchamber disposed between the first and the second end for depositing acatalyst material within interconnected pores of the interconnectedporous amorphous silicon layer, wherein the third chamber comprises: atarget having a surface in contact with a processing region, wherein thetarget comprises a catalytic material; and a power supply adapted todeliver energy to the target so that atoms from the surface of thetarget are deposited within the interconnected pores of theinterconnected porous amorphous silicon layer disposed in the processingregion.
 3. The apparatus of claim 2, further comprising: a fourthchamber disposed between the first and the second end, wherein thefourth chamber comprises: a hot filament adapted to be heated at asurface temperature higher than 1,500° C.; a showerhead that is adaptedto deliver a carbon containing source gas to form carbon nanotubes inthe interconnected pores of the interconnected porous amorphous siliconlayer using a hot wire chemical vapor deposition (HWCVD) process; andone or more gas sources coupled with the showerhead for delivering thecarbon containing source gas to the showerhead.
 4. The apparatus ofclaim 1, further comprising: a supply roll at the first end forsupplying the at least one continuous web of material to the chambersdisposed between the first end and the second end; and a take-up roll atthe second end for receiving the at least one continuous web of materialwith the energy storage device formed thereon.
 5. The apparatus of claim1, wherein the second chamber further comprises: a thrust plate disposedin the processing volume, substantially parallel to the anode assembly,wherein the thrust plate is positioned to hold a portion of the at leastone continuous web of conductive material in a position relative to theanode assembly during the anodization process.
 6. A high surface areaelectrode for use in an energy storage device, comprising: a substratehaving a conductive surface; and a porous amorphous silicon carbonnanotube composite based material deposited on the conductive surface,comprising: a porous amorphous silicon layer formed on the conductivesurface of the substrate, wherein the porous amorphous silicon layer hasa series of interconnected pores; and carbon nanotubes embedded withinthe series of interconnected pores of the porous amorphous siliconlayer.
 7. The high surface area electrode of claim 6, wherein the seriesof interconnected pores comprise a plurality of pores each having afirst diameter and extending from a top surface of the porous amorphoussilicon layer toward a bottom surface of the porous amorphous siliconlayer.
 8. The high surface area electrode of claim 7, wherein each ofthe plurality of pores is divided into multiple pores as the pluralityof pores extends toward the bottom surface of the porous amorphoussilicon layer, each of the multiple pores having a second diameter lessthan the first diameter.
 9. The high surface area electrode of claim 7,wherein each of the series of interconnected pores are divided intomultiple pores having a second diameter less than the first diameter ata series of branch structures as the series of interconnected poresextend toward the bottom surface of the porous amorphous silicon layer.10. The high surface area electrode of claim 6, wherein the series ofinterconnected pores extend from a top surface of the porous amorphoussilicon layer to a distance from about 10 nm to about 200 nm from abottom surface of the porous amorphous silicon layer.
 11. The highsurface area electrode of claim 6, wherein some of the carbon nanotubesembedded within the series of interconnected pores of the amorphoussilicon layer extend above a top surface of the amorphous silicon layer.12. The high surface area electrode of claim 9, wherein the firstdiameter is from about 500 nm to about 1,000 nm and the second diameteris from about 300 to about 400 nm.
 13. The high surface area electrodeof claim 6, wherein the substrate having a conductive surface is acontinuous web of conductive material comprising a material selectedfrom the group of copper (Cu), aluminum (Al), and nickel (Ni).
 14. Amethod of forming a high surface area electrode for use in an energystorage device, comprising: forming an amorphous silicon layer on acurrent collector having a conductive surface; immersing the amorphoussilicon layer in an electrolytic solution to form a series ofinterconnected pores in the amorphous silicon layer; and forming carbonnanotubes within the series of interconnected pores of the amorphoussilicon layer.
 15. The method of claim 14, wherein the immersing theamorphous silicon layer in an electrolytic solution further comprisespassing a current through the electrolytic solution with a metalelectrode disposed in the electrolytic solution serving as an anode andthe current collector having a conductive surface serving as a cathode.16. The method of claim 14, wherein the immersing the amorphous siliconlayer in an electrolytic solution further comprises: exposing theamorphous silicon layer to a first voltage to form a first set of poresof the series of interconnected pores having a first pore size in theamorphous silicon layer; and decreasing the first voltage to a secondvoltage to split each of the first set of pores into multiple poreshaving a second pore size that is smaller than the first pore size. 17.The method of claim 14, wherein the immersing the amorphous siliconlayer in an electrolytic solution further comprises exposing theamorphous silicon layer to a voltage that decreases over time so thatthe size of the pores of the series of interconnected pores decreases asthe voltage decreases.
 18. The method of claim 14, wherein the amorphoussilicon layer is formed using plasma enhanced chemical vapor depositiontechniques or hot wire chemical vapor deposition techniques.
 19. Themethod of claim 14, wherein the amorphous silicon layer is formed bydepositing a nanocrystalline/polycrystalline layer and bombarding thenanocrystalline/polycrystalline layer with ions.
 20. The method of claim14, wherein the carbon nanotubes are formed using one or more catalystmaterials selected from a group consisting of iron, cobalt, nickel,copper, silver, magnesium, ruthenium, rhodium, iridium, platinum,palladium, molybdenum, tungsten, chromium, and alloys and oxidesthereof.